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1
General Mole Balance
Rj
V
Q0 Q1
cj0 cj1
Conservation of mass
rate of ( ) ( )
rate of inflow rate of outflow
accumulation = −
of component j
of component j of component j
rate of generation
+ of component j by (1)
chemical reactions
2
General Mole Balance
Rj
V
Q0 Q1
cj0 cj1
Conservation of mass
d
Z Z
cj dV = Q0cj0 − Q1cj1 + Rj dV (2)
dt V V
3
General Mole Balance
d
Z Z
cj dV = Q0cj0 − Q1cj1 + Rj dV
dt V V
• Assuming component j enters and leaves the volume element only by con-
vection with the inflow and outflow streams, i.e. neglecting diffusional flux
through the boundary of the volume element due to a concentration gradient.
• The diffusional flux will be considered during the development of the material
balance for the packed-bed reactor.
4
Rate expressions
• To solve the reactor material balance, we require an expression for the pro-
duction rates, Rj
X
Rj = νij ri
i
5
The Batch Reactor
Rj
6
Batch Reactor
d
Z Z
cj dV = Q0cj0 − Q1cj1 + Rj dV
dt V V
• Because the reactor is well stirred, the integrals in Equation 2 are simple to
evaluate, Z Z
cj dV = cj VR Rj dV = Rj VR
VR VR
7
Reactor Volume
dcj
= Rj (4)
dt
• Use Equation 3 rather than Equation 4 if the reactor volume changes signifi-
cantly during the course of the reaction.
8
Analytical Solutions for Simple Rate Laws
9
First-order, irreversible
k
A -→ B, r = kcA (5)
dcA
= −kcA (6)
dt
10
First-order, irreversible
cA = cA0e−kt (7)
11
First-order, irreversible
12
1
0.8
0.6
cA
cA0
0.4 k = 0.5
k=1
0.2 k=2
k=5
0
0 1 2 3 4 5
t
13
First-order, irreversible
• The A concentration decreases exponentially from its initial value to zero with
increasing time.
• The rate constant determines the shape of this exponential decrease. Rear-
ranging Equation 7 gives
ln(cA/cA0) = −kt
14
First-order, irreversible
k = 0.5
k=1
0.1
k=2
cA
cA0
0.01
k=5
0.001
0 1 2 3 4 5
t
• One can get an approximate value of the rate constant from the slope of the
straight line.
15
• This procedure is a poor way to determine a rate constant and should be
viewed only as a rough approximation (Chapter 9).
16
First-order, irreversible
dcB
= RB = kcA (8)
dt
d(cA + cB )
= RA + RB = 0
dt
Therefore, cA + cB is a constant.
17
First-order, reversible
cA + cB = cA0 + cB0
18
First-order, reversible
k1
-*- B
A) (11)
k−1
dcA
= −r = −k1 cA + k−1 cB cA (0) = cA0
dt
dcB
= r = k1 cA − k−1 cB cB (0) = cB0
dt
19
First-order, reversible
dcA
= −k1cA + k−1(cA0 + cB0 − cA) (12)
dt
• Separation!
20
First-order, reversible
dcA
= acA + b
dt
Z cA Zt
dcA
= dt
cA0 acA + b 0
cA
1
ln(acA + b) =t
a
cA0
b
cA = cA0eat − (1 − eat )
a
21
First-order, reversible
−(k1 +k−1 )t k1 h
−(k1 +k−1 )t
i
cB = cB0e + (cA0 + cB0) 1 − e (14)
k1 + k−1
22
First-order, reversible
0.8 cA (t)
0.6 cBs
c
0.4 cAs
0.2 cB (t)
0
0 1 2 3 4 5
t
23
Nonzero steady state
k−1
cAs = (cA0 + cB0)
k1 + k−1
24
Nonzero steady state
1
cAs = (cA0 + cB0)
1 + K1
K1
cBs = (cA0 + cB0)
1 + K1
25
Second-order, irreversible
k
A -→ B (15)
2
in which the rate expression is second order, r = kcA .
dcA 2
= −kcA , cA(0) = cA0 (16)
dt
26
Second-order, irreversible
• Separation works here
dcA
2 = −kdt
cA
Z cA Zt
dcA
2 = −k dt
cA0 cA 0
1 1
− = −kt
cA0 cA
• Check that this solution satisfies the differential equation and initial condition
27
Second-order, irreversible
1
0.9
0.8
0.7
0.6
cA
0.5
cA0
0.4 second order
0.3
0.2 first order
0.1
0
0 1 2 3 4 5
• The second-order reaction decays more slowly to zero than the first-order
reaction.
28
Another second-order, irreversible
k
A + B -→ C r = kcAcB (18)
dcA
= −r = −kcAcB (19)
dt
dcB
= −r = −kcAcB (20)
dt
d(cA − cB )
=0
dt
29
Another second-order, irreversible
dcA
= −kcA(cA − cA0 + cB0)
dt
• This equation also is separable and can be integrated to give (you should
work through these steps),
−1
cB0 (cB0−cA0)kt
cA = (cA0 − cB0) 1 − e , cA0 ≠ cB0 (22)
cA0
30
Another second-order, irreversible
cA0 (cA0−cB0)kt −1
cB = (cB0 − cA0) 1 − e (23)
cB0
dcC
= kcAcB
dt
cC = cA0 − cA + cC0
31
Another second-order, irreversible
• Notice that if cA0 > cB0 (Excess A), the steady state
cAs = 0
cBs = cB0 − cA0
cCs = cA0 + cC0
32
nth-order, irreversible
n
The nth-order rate expression r = kcA
33
5
4.5
4 n=3
3.5 2
3
r 2.5
1
2
1/2
1.5
0
1
0.5
0
0 0.5 1 1.5 2 2.5 3
cA
34
nth-order, irreversible
k n
A -→ B r = kcA
dcA n
= −r = −kcA
dt
dcA
n = −kdt
cA
h i 1
−n+1 −n+1
cA = cA0 + (n − 1)kt , n≠1
35
nth-order, irreversible
cA 1
= [1 + (n − 1)k0t] −n+1 , n≠1 (24)
cA0
in which
n−1
k0 = kcA0
has units of inverse time.
36
nth-order, irreversible
0.8
0.6
cA
n=5
cA0
0.4 4
3
0.2 2
1
0
0 1 2 3 4 5
t
• The larger the value of n, the more slowly the A concentration approaches
zero at large time.
37
nth-order, irreversible
0.8
0.6
cA
cA0 n=2
0.4
1
0.2 1/2
0
−2 −1 −1/2
0
0 0.5 1 1.5 2
t
38
Negative order, inhibition
• For n < 0, the rate decreases with increasing reactant concentration; the
reactant inhibits the reaction.
5
4.5
4
3.5
3
r 2.5 n=−2
2 −1
1.5 −1/2
1
0
0.5
0
0 0.5 1 1.5 2 2.5 3
cA
39
Negative order, inhibition
• Inhibition reactions are not uncommon, but watch out for small concentra-
tions. Notice the rate becomes unbounded as cA approaches zero, which is
not physically realistic.
• When using an ODE solver we may modify the right-hand sides of the material
balance
n
(
dcA −kcA , cA > 0
=
dt 0, cA = 0
40
Two reactions in series
• Consider the following two irreversible reactions,
k1
A -→ B (25)
k2
B -→ C (26)
• Let the reaction rates be given by simple first-order rate expressions in the
corresponding reactants,
r1 = k1cA
r2 = k2cB
41
Two reactions in series
dcA
= RA = −r1 = −k1cA
dt
dcB
= RB = r1 − r2 = k1cA − k2cB
dt
dcC
= RC = r2 = k2cB
dt
42
Two reactions in series – B
dcB
+ k2cB = k1cA0e−k1t
dt
k 1
h i
cB = cB0e−k2t + cA0 e−k1t − e−k2t , k1 ≠ k2 (27)
k2 − k1
43
Two reactions in series – C
44
Two reactions in series
0.8
cA (t) cC (t)
0.6
cB (t)
c
0.4
0.2
0
0 1 2 3 4 5
t
45
Two reactions in parallel
k1
A -→ B (28)
k2
A -→ C (29)
• Assume the rates of the two irreversible reactions are given by r1 = k1cA and
r 2 = k 2 cA .
46
Two reactions in parallel
dcA
= RA = −r1 − r2 = −k1cA − k2cA
dt
dcB
= R B = r1 = k 1 cA
dt
dcC
= R C = r2 = k 2 cA
dt
47
Two reactions in parallel
cA = cA0e−(k1+k2)t (30)
dcB
= k1cA0e−(k1+k2)t
dt
k1 −(k1 +k2 )t
cB = cB0 + cA0 1−e (31)
k1 + k2
48
Two reactions in parallel
k2 −(k1 +k2 )t
cC = cC0 + cA0 1−e (32)
k1 + k2
49
Two reactions in parallel
0.8
cA (t) cC (t)
0.6
c
0.4 cB (t)
0.2
0
0 0.5 1 1.5 2 2.5 3
t
50
Two reactions in parallel
• Notice that the two parallel reactions compete for the same reactant, A
51
Conversion, Yield, Selectivity
There are several ways to define selectivity, yield and conversion, so be clear
about the definition you choose.
Point selectivity: The point (or instantaneous) selectivity is the ratio of the production rate of
one component to the production rate of another component.
Overall selectivity: The overall selectivity is the ratio of the amount of one component pro-
duced to the amount of another component produced.
Yield: The yield of component j is the fraction of a reactant that is converted into component
j.
Conversion: Conversion is normally defined to be the fraction of a component that has been
converted to products by the reaction network. Conversion has several definitions and
conventions. It is best to state the definition in the context of the problem being solved.
52
The Continuous-Stirred-Tank Reactor (CSTR)
Qf Q
cjf Rj cj
53
CSTR – Constant Density
• If the reactor volume is constant and the volumetric flowrates of the inflow
and outflow streams are the same, Equation 33 reduces to
dcj 1
= (cjf − cj ) + Rj (34)
dt τ
• The parameter
τ = VR /Qf
is called the mean residence time of the CSTR.
54
CSTR – Steady State
• The steady state of the CSTR is described by setting the time derivative in
Equation 33 to zero,
0 = Qf cjf − Qcj + Rj VR (35)
Qf cjf − Qcj
xj = (steady state) (36)
Qf cjf
55
Transient behavior of the CSTR
k
A -→ 2B r = kcA
the feed concentration of A is cAf = 2 mol/L, the residence time of the reactor
is τ = 100 min, and the rate constant is k = 0.1 min−1.
1. Find the steady-state concentration of A in the effluent for the given feed.
2. Plot the concentration of A versus time for constant feed concentration cAf = 2 mol/L if
the reactor is initially filled with an inert so cA0 = 0 mol/L.
3. Plot the concentration of A versus time for constant feed concentration cAf = 2 mol/L if
the reactor is initially filled with feed so cA0 = 2 mol/L.
56
Transient CSTR Solution. Part 1
cA = cAf + RAτ
• Substituting the production rate RA = −kcA and solving for cA gives the
steady-state concentration
cAf
cAs =
1 + kτ
2 mol/L
cAs = = 0.182 mol/L
1 + (0.1 min−1)(100 min)
57
Parts 2 and 3
dcA 1
= cAf − cA − kcA (38)
dt τ
cA(0) = cA0
58
Parts 2 and 3
1 cA0 = 2
0.5
cAs = 0.182
cA0 = 0
0
0 10 20 30 40 50 60 70 80
t (min)
• Both solutions converge to the same steady-state even though the starting
conditions are quite different.
59
Phenol production in a CSTR
r = kcCHP
• Find the reactor volume to achieve 85% conversion of CHP at steady state.
The flowrate into the reactor is Qf = 26.9 m3/hr and k = 4.12 hr−1.
60
Phenol production
cA = cAf + RAτ
cAf
cA = (42)
1 + kτ
61
Phenol production
cAf − cA cA
xA = =1−
cAf cAf
kτ
xA =
1 + kτ
1 xA
τ=
k 1 − xA
62
Phenol production
Qf xA
VR =
k(1 − xA)
(26.9 m3/hr)(0.85)
VR = = 37 m3
(4.12 hr−1)(0.15)
63
The Semi-Batch Reactor
• The semi-batch reactor is a cross between the batch reactor and CSTR.
• The semi-batch reactor is initially charged with reactant, like the batch reac-
tor, but allows a feed addition policy while the reaction takes place, like the
CSTR.
64
The Semi-Batch Reactor
• One may choose to operate a semi-batch reactor to control the reaction rate
or heat release during reaction by slowly adding one of the reactants in the
feed stream.
• Compared to the batch reactor, the semi-batch reactor provides more com-
plete use of the reactor volume in reactions such as polymerizations that
convert from lower density to higher density during the course of the reac-
tion.
65
Volume Change Upon Reaction
d cj VR
= Qf cjf − Qcj + Rj VR (44)
dt
• Equation 44 covers both the batch, CSTR and semi-batch reactors, depending
on how we specify Qf and Q.
P
• The term j cj Mj is simply the mass density of the reactor contents, which
66
we denote ρ
ns
X
ρ= cj M j (46)
j=1
67
Volume Change Upon Reaction
P
• The term j cjf Mj is the mass density of the feedstream, ρf .
P
• We know that conservation of mass in chemical reactions implies j Rj Mj = 0
(see Chapter 2). Substitution into Equation 45 leads to
d(ρVR )
= Qf ρf − Qρ (47)
dt
• Equation 47 is clearly a total mass balance, in which the total mass in the
reactor changes in time due to the inflow and outflow of mass.
• Notice that chemical reactions play no role in the total mass balance.
68
Equation of state for the mixture
• This relationship is one form of the equation of state for the mixture
69
Equation of state for the mixture
• For example, we could express the equation of state in terms of the partial
molar volumes as X
cj V j = 1
j
70
Equation of state for the mixture — Ideal mixture
X
cj Vj◦ = 1, ideal mixture
j
71
Constant density
ρ = ρf (48)
dVR
= Qf − Q (49)
dt
72
Constant density
dVR
= Qf − Q
dt
• CSTR (dynamic and steady state). If the outflow of the CSTR is regulated so
that the CSTR has constant volume, then we can conclude from Equation 49
that Q = Qf .
73
Nonconstant density
Unknowns.
• In the general case, consider the following variables to fully determine the
state of the reactor: T , P , nj , VR .
• We also require the value of Q to specify the right-hand sides of the material
balances.
• The set of unknowns is nj , VR , Q.
• We therefore have ns + 2 unknowns.
Equations.
74
Nonconstant density – reactor operation
75
Nonconstant density – reactor operation
P
j fj cjf
P
dVR i ∆fi ri VR
= Qf P −Q+ P (50)
dt f c
j j j j f j cj
• in which fj is
∂f
fj =
∂cj
• and ∆fi is
X X ∂f
∆fi = νij fj = νij
j j
∂cj
which is a change in a derivative property upon reaction.
76
Nonconstant density – idea mixture
cj Vj◦ − 1 = 0.
P
• For the ideal mixture we have f (cj ) = j
fj = Vj◦
the pure component specific volumes
dVR X
= Qf − Q + ∆Vi◦riVR
dt i
77
Nonconstant density
dnj
Component balances: = Qf cjf − Qcj + Rj VR , j = 1, . . . , ns
dt
∆V ◦ = ◦
P P
Defined quantities: nj = cj VR ρ= j cj Mj j νij Vj
i
VR = VR0 Q = Qf VR = VR0 Q = Qf +
P ◦
1. vol i ∆Vi ri VR
dVR
= Qf (1 − ρf /ρ) + i ∆V ◦ ri VR
P
2. mass VR = VR0 Q = Qf Q = Qf ρf /ρ
dt i
dVR dVR
= Qf − Q + i ∆V ◦ ri VR
P
3. Q = Qf − Q Q specified Q specified
dt dt i
78
Nonconstant density
dnj
Component balances: = Qf cjf − Qcj + Rj VR , j = 1, . . . , ns
dt
P P ∂f
Defined quantities: nj = cj VR ρ= j cj Mj ∆fi = j νij ∂c
j
DAEs ODEs
P
j fj cjf
P
1. vol VR = VR0 f (cj ) = 0 VR = VR0 Q = Qf P + Pi ∆fi ri VR
j fj cj j fj cj
P
fj cjf
P
2. mass ρVR = ρ0 VR0 f (cj ) = 0
dVR
= Qf P
j
−Q+ Pi ∆fi ri VR Q = Qf ρf /ρ
dt j fj cj j f j cj
P
j fj cjf
P
3. Q Q specified f (cj ) = 0
dVR
= Qf P −Q+ Pi ∆fi ri VR Q specified
dt j fj cj j f j cj
79
Semi-batch polymerization
k
M -→ P r = kcM
80
Semi-batch polymerization
1. The monomer feed is shut off and the reaction goes to completion.
2. The monomer feed is adjusted to keep the reactor filled while the reaction
goes to completion.
• Calculate the total polymer mass production, and the percentage increase in
polymer production achieved in the second operation.
81
The physical properties
82
Semi-batch polymerization
d(cM VR )
= Qf 0cMf − kcM VR
dt
in which cMf = ρM /MM is given, and Qf = Qf 0 is constant during the filling
operation.
dM
= Qf 0cMf − kM (51)
dt
M(0) = 0
83
Semi-batch polymerization
dVR
= Qf 0 + ∆V kM (52)
dt
VR (0) = 10 m3
84
The polymer mass production
• To compute the polymer mass, we note from the stoichiometry that the mass
production rate of polymer R
e P is
R
e P = −RM MM
dPe
=R
e p VR = kcM MM VR = (kMM )M (53)
dt
85
Semi-batch polymerization
• The text solves this problem analytically. Instead, let’s solve it numerically.
• We need an ODE solver that is smart enough to stop when the reactor fills,
because we do not know this time t1. The ODE solver needs to find it for us.
• dasrt is an ODE solver with the added capability to find the time at which
some event of interest occurs.
86
Finding the time for filling the reactor
t1 = 11.2 min
• Note the reactor would have filled in 10 min if the density were constant.
• The extra time reflects the available volume created by converting some of
the monomer to polymer during filling.
87
Operation 1.
88
Semi-batch polymerization
89
2
20
1
VR (m3 ) 15
10
0 10 20 30 40 50
time (min)
90
1
0.8
Qf (m3 /min)
0.6
0.4
0.2 2
0
1
-0.2
0 10 20 30 40 50
time (min)
Figure 5: Semi-batch reactor feed flowrate for primary monomer addition (op-
eration 1) and primary plus secondary monomer additions (operation 2).
91
6000
5000
monomer (kg)
4000
3000
2
2000
1000 1
0
0 10 20 30 40 50
time (min)
92
12000
10000 2
polymer (kg)
8000 1
6000
4000
2000
0
0 10 20 30 40 50
time (min)
93
Operation 2.
• Because the reactor volume is constant, we can solve Equation 52 for the feed
flowrate during the secondary monomer addition
Qf = −∆V kM
94
Polymer production rate
• We can perform an independent, simple calculation of the total polymer in
operation 2. Useful for debugging the computation.
Pe2 − Pe1
× 100% = 22.5%
P1
e
95
• By using the volume of the reactor more efficiently, the total polymer produc-
tion increases 22.5%.
96
The Plug-Flow Reactor (PFR)
• Plug flow in a tube is an ideal-flow assumption in which the fluid is well mixed
in the radial and angular directions.
• The fluid velocity is assumed to be a function of only the axial position in the
tube.
• Plug flow is often used to approximate fluid flow in tubes at high Reynolds
number. The turbulent flow mixes the fluid in the radial and angular direc-
tions.
97
Thin Disk Volume Element
Given the plug-flow assumption, it is natural to take a thin disk for the reactor
volume element
Qf Q
cjf cj
z }| {
z z + ∆z
98
Thin Disk Volume Element
• Dividing the above equation by ∆V and taking the limit as ∆V goes to zero
yields,
∂cj ∂ cj Q
=− + Rj (55)
|∂t
{z } | ∂V |{z}
{z } reaction
accumulation convection
99
Length or volume as independent variable
• If the tube has constant cross section, Ac , then velocity, v, is related to vol-
umetric flowrate by v = Q/Ac , and axial length is related to tube volume by
z = V /Ac ,
100
Steady-State Operation
d(cj Q)
= Rj (57)
dV
• The product cj Q = Nj is the total molar flow of component j. One also can
express the PFR mole balance in terms of the molar flow,
dNj
= Rj (58)
dV
101
Volumetric Flowrate for Gas-Phase Reactions
• The important piece of information tying these quantities together is, again,
the equation of state for the reaction mixture, f (T , P , cj ) = 0.
N j = cj Q (59)
102
Ideal Gas Equation of State
• One can solve the previous equation for the volumetric flowrate,
RT X
Q= Nj (60)
P j
103
Ideal Gas Equation of State
• To evaluate the concentrations for use with the reaction rate expressions, one
simply rearranges Equation 59 to obtain
Nj P Nj
cj = = P (61)
Q RT j Nj
104
Volumetric Flowrate for Liquid-Phase Reactions
• Consider the equation of state for a liquid-phase system to be arranged in
the form
ρ = f (T , P , cj )
• The mass density is related to the volumetric flowrate and total mass flow,
P
M = j Nj Mj , via
M = ρQ (62)
dM
= 0, M(0) = Mf
dV
105
Volumetric Flowrate for Liquid-Phase Reactions
Mf
Q= (63)
ρ
and the volumetric flowrate is constant and equal to the feed value.
106
Volumetric Flowrate for Liquid-Phase Reactions
dcj
= Rj , constant flowrate (65)
dτ
• For the constant-flowrate case, the steady-state profile in a PFR starting from
a given feed condition is also the transient profile in a batch reactor starting
from the equivalent initial condition.
107
Single Reaction Systems – Changing flowrate in a PFR
k
A -→ B + C (66)
• The reaction rate is first order in A, k = 0.05 sec−1 at the reactor temperature,
and the feed flowrate is 35 L/min.
108
Changing flowrate in a PFR
• The mole balance for component A gives
dNA
= RA
dV
dNA
= −kNA/Q (67)
dV
• The volumetric flowrate is not constant, so we use Equation 60, which as-
sumes an ideal-gas equation of state,
RT
Q= (NA + NB + NC) (68)
P
109
Changing flowrate in a PFR
• The ideal-gas assumption is reasonable at this reactor temperature and pres-
sure.
• One can relate the molar flows of B and C to A using the reaction stoichiom-
etry. The mole balances for B and C are
dNB dNC
= RB = r = RC = r
dV dV
• The stoichiometry does not allow the molar flow NA +NB or NA +NC to change
with position in the tube.
110
Changing flowrate in a PFR
• Because NA + NB and NB + NC are known at the tube entrance, one can relate
NB and NC to NA,
NA + NB = NAf + NBf
NA + NC = NAf + NCf
NB = NAf + NBf − NA
NC = NAf + NCf − NA
RT
Q= 2NAf + NBf + NCf − NA
P
111
Changing flowrate in a PFR
RT
Q= 2NAf − NA
P
dNA P NA
= −k
dV RT 2NAf − NA
112
Changing flowrate in a PFR
RT
V =− NAf [2 ln(1 − xA) + xA]
kP
113
Changing flowrate in a PFR
Qf
z=− [2 ln(1 − xA) + xA]
kAc
114
Multiple-Reaction Systems
• The modeler has some freedom in setting up the material balances for a plug-
flow reactor with several reactions.
• The most straightforward method is to write the material balance relation for
every component,
dNj
= Rj , j = 1, 2, . . . , ns
dV
nr
X
Rj = νij ri, j = 1, 2, . . . , ns
i=1
115
Benzene pyrolysis in a PFR
• Hougen and Watson [3] analyzed the rate data for the pyrolysis of benzene
by the following two reactions.
k1
-*- C12H10 + H2
2C6H6 )
k−1
2B -*-
) D + H
116
Benzene pyrolysis in a PFR
k2
-*- C18H14 + H2
C6H6 + C12H10 ) (69)
k−2
B + D -*-
) T + H (70)
• The reactions are assumed to be elementary so that the rate expressions are
c c
D H
r1 = k1 cB2 − (71)
K1
cT cH
r2 = k2 cB cD − (72)
K2
117
Benzene pyrolysis in a PFR
• Calculate the tube volume required to reach 50% total conversion of the ben-
zene for a 60 kmol/hr feed stream of pure benzene.
• Plot the mole fractions of the four components versus reactor volume.
118
Benzene pyrolysis in a PFR
• The rate and equilibrium constants at T = 1033K and P = 1.0 atm are given
in Hougen and Watson,
k1 = 7 × 105 L/mol · hr
k2 = 4 × 105 L/mol · hr
K1 = 0.31
K2 = 0.48
119
Benzene pyrolysis in a PFR
• The mole balances for the four components follow from the stoichiometry,
dNB
= −2r1 − r2 (73)
dV
dND
= r1 − r2 (74)
dV
dNH
= r1 + r2 (75)
dV
dNT
= r2 (76)
dV
• The initial condition for the ODEs are NB (0) = NBf and ND (0) = NH (0) =
NT (0) = 0.
120
Benzene pyrolysis in a PFR
• The total molar flux does not change with reactor volume.
RT
Q= NBf (77)
P
• The rate expressions are substituted into the four ODEs and they are solved
numerically.
121
0.6
0.5
0.4
xB 0.3
0.2
0.1
0
0 200 400 600 800 1000 1200 1400 1600
V (L)
122
1
0.8
0.6 yB
yj
0.4
yH
0.2 yD
yT
0
0 200 400 600 800 1000 1200 1400 1600
V (L)
123
Ethane pyrolysis in the presence of NO
124
Some PFR-CSTR Comparisons
• We have two continuous reactors in this chapter: the CSTR and the PFR.
k n
A -→ B r = kcA (78)
• For this situation, the steady-state PFR material balance is given by Equa-
tion 65
dcA
= −r (cA)
dτ
125
Some PFR-CSTR Comparisons
• We rearrange and solve for the time required to change from the feed condi-
tion cAf to some exit concentration cA
Z cA
1 0
τ= dc
cAf r (cA0
) A
0
• The area under the curve 1/r (cA ) is the total time required to achieve the
desired concentration change.
1 CSTR
0
r (cA )
PFR
cA 0 cAf
cA
126
Some PFR-CSTR Comparisons
• To achieve this same concentration change in the CSTR, we start with Equa-
tion 37, and solve for τ giving
cAf − cA
τ=
r (cA)
• This result also can be interpreted as an area. Notice that this area is the
height, 1/r (cA), times the width, cAf − cA, of the rectangle.
1 CSTR
0
r (cA )
PFR
cA 0 cAf
cA
127
Some PFR-CSTR Comparisons
• The PFR reaction rate varies with length. The rate is high at the entrance to the
tube where the concentration of A is equal to the feed value, and decreases
with length as the concentration drops. At the exit of the PFR, the rate is the
lowest of any location in the tube.
• Now considering that the entire volume of the CSTR is reacting at this lowest
rate of the PFR, it is intuitively obvious that more volume is required for the
CSTR to achieve the same conversion as the PFR.
128
Some PFR-CSTR Comparisons
• If the reaction order is positive (the usual case), the PFR is more efficient. If
the reaction order is negative, the CSTR is more efficient.
1 PFR
0
r (cA )
CSTR
cA 0 cAf
cA
129
The PFR versus CSTR with separation
• The PFR achieves higher conversion than an equivalent volume CSTR for the
irreversible reaction with first-order kinetics
A -→ B r = kcA
• Find a single CSTR and separator combination that achieves the same con-
version as the PFR.
130
The PFR versus CSTR with separation
131
The PFR versus CSTR with separation
NA0 NA
VR
VR
αNA2 αNA2
pure B
• In the text, we show how to find the recycle flowrate so this system achieves
the PFR conversion.
132
CSTR Equivalence Principle.
• This example was motivated by a recent result of Feinberg and Ellison called
the CSTR Equivalence Principle of Reactor-Separator Systems [2].
133
Stochastic Simulation of Chemical Reactions
• We will see that the deterministic rate laws and material balances presented in
the previous sections can be captured in the stochastic approach by allowing
the numbers of molecules in the simulation to become large.
134
Stochastic Simulation of Chemical Reactions
135
Stochastic Simulation of Chemical Reactions
• Assume we have only a hundred molecules moving randomly in the gas phase
k1
A -→ B (79)
k2
B -→ C (80)
r1 = k1xA r2 = k2 xB
136
Stochastic Simulation of Chemical Reactions
• The basic idea of the Gillespie algorithm is to: (i) choose randomly the time
at which the next reaction occurs, and (ii) choose randomly which reactions
occurs at that time.
1. Initialize. Set integer counter n to zero. Set the initial species numbers,
xj (0), j = 1, . . . ns . Determine stoichiometric matrix ν and reaction probabil-
ity laws (rate expressions)
ri = kih(xj )
for all reactions.
137
Stochastic Simulation of Chemical Reactions
3. Select two random numbers, p1, p2, from a uniform distribution on the inter-
val (0, 1). Let the time interval until the next reaction be
te = − ln(p1)/rtot (81)
138
Stochastic Simulation of Chemical Reactions
r1 r2
0 r1 +r2 r1 +r2 1
139
Stochastic Simulation of Chemical Reactions
5. Update the simulation time t(n + 1) = t(n) + te. Update the species numbers
for the single occurrence of the mth reaction via
xj (n + 1) = xj (n) + νmj , j = 1, . . . ns
140
Stochastic Simulation of Chemical Reactions
• If rtot is the total probability for reaction, e−rtot t is the probability that a re-
e
• The next figure shows the results of this algorithm when starting with xA =
100 molecules.
141
Stochastic Simulation of Chemical Reactions
142
100
80
xC
xA
60
xB
xj
40
20
0
0 1 2 3 4 5
t
143
Stochastic Simulation of Chemical Reactions
• Notice the random aspect of the simulation gives a rough appearance to the
number of molecules versus time, which is quite unlike any of the determin-
istic simulations.
• But in spite of the roughness, we already can make out the classic behavior
of the series reaction: loss of starting material A, appearance and then dis-
appearance of the intermediate species B, and slow increase in final product
C.
144
Stochastic Simulation of Chemical Reactions
145
Stochastic Simulation of Chemical Reactions
146
1000
800
xC
xA
600
xB
xj
400
200
0
0 1 2 3 4 5
t
147
Stochastic Simulation of Chemical Reactions
148
4000
3200
xC
xA
2400
xB
xj
1600
800
0
0 1 2 3 4 5
t
149
Stochastic Simulation of Chemical Reactions
• We see the random fluctuations become less pronounced. Notice that even
with only 4000 starting molecules, the results compare very favorably with
the deterministic simulation shown previously.
• Another striking feature of the stochastic approach is the trivial level of pro-
gramming effort required to make the simulations.
150
Hepatitis B virus modeling
151
Hepatitis B virus modeling
cccDNA
nucleotides −−
−−
−−→ rcDNA (82)
nucleotides + rcDNA −−
−−
−−→ cccDNA (83)
cccDNA
amino acids −−
−−
−−→ envelope (84)
cccDNA −−
−−
−−→ degraded (85)
envelope −−
−−
−−→ secreted or degraded (86)
rcDNA + envelope −−
−−
−−→ secreted virus (87)
152
Hepatitis B virus modeling
• The reaction rates and production rates for Reactions 82–87 are given by
r1 k1 xA
r2 k2 xB
R r − r4
A 2
r3 k3 xA
RB = r1 − r2 − r6
= (88)
r4 k4 xA
RC r3 − r5 − r6
r5
k5xC
r6 k6xB xC
153
Hepatitis B virus modeling
• Assume the systems starts with a single cccDNA molecule and no rcDNA and
no envelope protein, and the following rate constants
h iT h iT
xA xB xC = 1 0 0 (89)
h i
T −6
k = 1 0.025 1000 0.25 2 7.5 × 10 (90)
154
Average stochastic is not deterministic.
25
20
cccDNA
15
deterministic
10
avg. stochastic
5
0
0 50 100 150 200
t (days)
250
200
rcDNA
150 deterministic
100
avg. stochastic
50
0
0 50 100 150 200
t (days)
155
10000
8000
envelope
6000 deterministic
4000 avg. stochastic
2000
0
0 50 100 150 200
t (days)
156
Hepatitis B virus modeling
157
35
30 stoch 1
25
20
cccDNA
15
10 deterministic
5
stoch 2
0
Figure 10: Species cccDNA versus time for hepatitis B virus model; two repre-
sentative stochastic trajectories.
158
Hepatitis B virus modeling
• Figure 10 shows two representative stochastic simulations for only the cc-
cDNA species.
• Notice the first stochastic simulation does fluctuate around the deterministic
simulation as expected.
159
Average stochastic is not deterministic.
• In fact, it occurs for 125 of the 500 simulations. So the average stochastic
simulation consists of 75% trajectories that fluctuate about the deterministic
trajectory and 25% trajectories that go to zero.
25
20
cccDNA
15
deterministic
10
avg. stochastic
5
0
0 50 100 150 200
t (days)
160
Summary
161
Summary
d(cj VR )
BATCH = Rj VR (91)
dt
dcj
constant volume = Rj (92)
dt
d(cj VR )
CSTR = Qf cjf − Qcj + Rj VR (93)
dt
dcj 1
constant density = (c − cj ) + Rj (94)
dt τ jf
d(cj VR )
SEMI-BATCH = Qf cjf + Rj VR (96)
dt
∂cj ∂(cj Q)
PFR = − + Rj (97)
∂t ∂V
d(cj Q)
steady state = Rj (98)
dV
dcj
constant flowrate = Rj , τ = V /Qf (99)
dτ
162
Summary
163
Summary
• Several of these simple mass balances with basic rate expressions were solved
analytically.
• In the case of multiple reactions with nonlinear rate expressions (i.e., not
first-order reaction rates), the balances must be solved numerically.
164
Summary
• We showed that the PFR achieves higher conversion than the CSTR of the
same volume if the reaction rate is an increasing function of a component
composition (n > 0 for an nth-order rate expression).
• Conversely, the CSTR achieves higher conversion than the same-volume PFR
if the rate is a decreasing function of a component composition (n < 0).
165
Summary
• The stochastic model uses basic probability to compute reaction rate. A given
reaction’s probability of occurrence is assumed proportional to the number
of possible combinations of reactants for the given stoichiometry.
• Two pseudo-random numbers are chosen to determine: (i) the time of the
next reaction and (ii) the reaction that occurs at that time.
166
References
[2] M. Feinberg and P. Ellison. General kinetic bounds on productivity and se-
lectivity in reactor-separator systems of arbitrary design: I. Principles. Ind.
Eng. Chem. Res., 40(14):3181–3194, 2001.
167